JP2018016918A - Sheet-like article and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheet-like article excellent in fog resistance and abrasion resistance and a manufacturing method therefor.SOLUTION: The sheet-like article contains a fibrous substrate consisting of an ultra fine fiber, and a polymer elastic body, the polymer elastic body binds an ultraviolet absorber by a covalent bond, the polymer elastic bodies bind each other by the covalent body, fog property is 85% or more and abrasion loss with 20,000 Martindale abrasion tests is 10 mg or less. The manufacturing method of the sheet-like article containing the fibrous substrate consisting of the ultra fine fiber, and the polymer elastic body, including a process for adding the polymer elastic body, the ultraviolet absorber and a bi- or higher functional compound to the fibrous substrate consisting of the ultra fine fiber and then heating them at 80°C to 200°C.SELECTED DRAWING: None

Description

  The present invention relates to a sheet-like material and a manufacturing method thereof.

  A sheet-like material composed mainly of a fibrous base material made of a fabric such as a nonwoven fabric and a polymer elastic body has excellent characteristics not found in natural leather, and is widely used for various uses such as artificial leather. . In particular, sheet-like materials using polyester fiber base materials have been used year by year for apparel, chair upholstery and automotive interior materials.

  In particular, in the field of automobile seats and automobile interior materials, the interior of the vehicle is exposed to sunlight, and the interior temperature is very high, so that excellent fogging characteristics are required. Here, the fogging property means that a slight amount of gas is generated in a high-temperature atmosphere from resinous materials (including artificial leather) used for automobile seats and automobile interior materials, and this is the front window and side. It has the characteristic about the phenomenon which fogs the glass of a window, and what has the robustness which does not produce such fogging is excellent in a fogging characteristic.

  In general, it is known that a polymer elastic body contained in a sheet-like material deteriorates by being exposed to sunlight for a long time, resulting in a decrease in physical properties. A technique of applying an agent is taken. However, many ultraviolet absorbers volatilize from the sheet-like material in a high temperature atmosphere, and fogging occurs.

  In order to solve this problem, a sheet-like material containing an ultraviolet absorbing polymer obtained by increasing the molecular weight of an ultraviolet absorber has been proposed (Patent Document 1).

  In addition, a technique has also been proposed in which an ultraviolet absorber is covalently bonded to the main chain of polyurethane by copolymerizing the ultraviolet absorber during polymerization of the polyurethane (Patent Document 2).

JP 2013-53206 A JP 2010-47675

  However, in the sheet-like material described in Patent Document 1, since a part of the polymer is thermally decomposed and reduced in molecular weight by being exposed to a high temperature atmosphere for a long time, the volatilization of the UV absorber is completely eliminated. It cannot be suppressed.

  Moreover, in the technique described in Patent Document 2, although the volatilization of the ultraviolet absorber can be suppressed, the amount of the ultraviolet absorber added according to the base material of the sheet-like material cannot be controlled, and the cost and design properties are low. From the viewpoint, it is difficult to apply to sheet-like materials such as artificial leather. Furthermore, although the sheet-like material has a problem that the fiber falls off due to a physical action such as friction depending on the application, it is difficult to improve the wear characteristics of the sheet-like material by the above technique.

  Therefore, an object of the present invention is to provide a sheet-like material excellent in fogging resistance and wear resistance, and a method for producing the same.

  The present invention is to achieve the above-described problems, and is a sheet-like material and a method for manufacturing the same, which are described below.

  The sheet-like material of the present invention is a sheet-like material comprising a fibrous base material composed of ultrafine fibers and a polymer elastic body, wherein the polymer elastic body is covalently bonded to an ultraviolet absorber, The molecular elastic bodies are bonded to each other by a covalent bond, the fogging characteristic is 85% or more, and the wear loss after 20,000 Martindale wear tests is 10 mg or less.

  Further, the method for producing a sheet-like product of the present invention is a method for producing a sheet-like product comprising a fibrous base material composed of ultrafine fibers and a polymer elastic body. It is a manufacturing method of a sheet-like thing including the process heated after giving a body, a ultraviolet absorber, and a compound more than bifunctional at 80 ° C-200 ° C.

  The sheet-like material of the present invention is excellent in fogging resistance and wear resistance. Moreover, the sheet-like material excellent in fogging resistance and wear resistance can be obtained by the method for producing a sheet-like material of the present invention.

A specific form for carrying out the present invention will be described next.
<Sheet>
The sheet-like material of the present invention is a sheet-like material comprising a fibrous base material composed of ultrafine fibers and a polymer elastic body, wherein the polymer elastic body is covalently bonded to an ultraviolet absorber, The molecular elastic bodies are bonded to each other by a covalent bond, the fogging characteristic is 85% or more, and the wear loss after 20,000 Martindale wear tests is 10 mg or less. In addition, in this specification, the fiber base material which consists of an ultrafine fiber may be described as a sheet | seat.

  As the fibrous base material composed of the ultrafine fibers, fabrics such as woven fabrics, knitted fabrics and nonwoven fabrics composed of ultrafine fibers can be preferably employed. Especially, since the surface quality of the sheet-like thing at the time of surface raising treatment is favorable, the nonwoven fabric which consists of an ultrafine fiber is used preferably. In the fibrous base material composed of the ultrafine fibers, a woven fabric, a knitted fabric, a nonwoven fabric and the like composed of the ultrafine fibers can be appropriately laminated and used together.

  When a non-woven fabric made of ultrafine fibers is used as the fibrous base material made of ultrafine fibers, both short fiber non-woven fabrics and long fiber non-woven fabrics can be used, but short fibers are obtained in that surface quality consisting of a uniform raised length can be obtained. Nonwoven fabric is preferably used.

  The fiber length of the short fiber in the short fiber nonwoven fabric is preferably 25 mm to 90 mm, more preferably 35 mm to 75 mm. By setting the fiber length to 25 mm or more, it becomes easy to obtain a sheet-like material having excellent wear resistance due to entanglement. Moreover, by making the fiber length 90 mm or less, it becomes easier to obtain a sheet-like product with better quality.

  The ultrafine fibers constituting the fibrous base material composed of the ultrafine fibers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate and polylactic acid, polyamides such as 6-nylon and 66-nylon, acrylic, polyethylene, Ultrafine fibers made of a thermoplastic resin that can be melt-spun such as polypropylene and thermoplastic cellulose can be used. Among these, ultrafine fibers made of polyester are preferably used from the viewpoint of strength, dimensional stability, and light resistance. Moreover, as a fibrous base material which consists of an ultrafine fiber, it is accept | permitted that the ultrafine fiber of a different raw material is mixed and comprised.

  The cross-sectional shape of the ultrafine fiber is preferably a round cross-section from the viewpoint of processing operability, but is polygonal such as an ellipse, flat and triangular, fan-shaped and cross-shaped, hollow-shaped, Y-shaped, T-shaped , And U-shaped and other irregular cross-sections can be used.

  Moreover, it is preferable that the average fiber diameter of the single fiber of the ultrafine fiber which comprises the fibrous base material which consists of the said ultrafine fiber is 0.1-7 micrometers, More preferably, it is 0.3-5 micrometers. By making the average fiber diameter of the single fibers 7 μm or less, the tactile sensation of the fibrous base material made of ultrafine fibers becomes more flexible. On the other hand, when the average fiber diameter of the single fibers is 0.1 μm or more, the color developability after dyeing is further improved.

  When the fibrous base material made of ultrafine fibers is a non-woven fabric made of ultrafine fibers, woven fabrics and knitted fabrics made of fibers that are not ultrafine fibers can be combined for the purpose of improving the strength. Especially, it is a preferable aspect to use a textile fabric from a viewpoint which can expect form stability improvement and strength improvement. In the present invention, when the term “woven fabric” or “knitted fabric” is simply used, it refers to a woven fabric or a knitted fabric made of fibers that are not ultrafine fibers. Moreover, when combining the nonwoven fabric which consists of an ultrafine fiber, a woven fabric, and a knitted fabric, the whole which combined the nonwoven fabric consisting of an ultrafine fiber, a fabric, and a knitted fabric is called the fibrous base material which consists of an ultrafine fiber. The combination of a nonwoven fabric made of ultrafine fibers and a woven fabric or knitted fabric is any combination of a woven fabric or knitted fabric laminated on a nonwoven fabric made of ultrafine fibers, or a combination in which a woven fabric or knitted fabric is inserted into a nonwoven fabric made of ultrafine fibers. Can also be adopted.

  Single yarns (warps and wefts) constituting woven fabrics and knitted fabrics include single yarns made of synthetic fibers such as polyester fibers and polyamide fibers. From the standpoint of fastness to dyeing, ultrafine fibers constituting the fibrous base material A preferred embodiment is a single yarn made of fibers of the same material.

  Examples of the form of such a single yarn include filament yarn and spun yarn, but these strongly twisted yarns are preferably used. In addition, filament yarn is preferably used for the spun yarn because the fluff of the surface fluff may be caused.

  When using a strongly twisted yarn, the number of twists is preferably 1000 T / m or more and 4000 T / m or less, and more preferably 1500 T / m or more and 3500 T / m or less. When the number of twists is less than 1000 T / m, the number of single fibers constituting the strongly twisted yarn by needle punching increases, and the physical properties of the product tend to deteriorate and the exposure of the single fibers to the product surface tends to increase. Moreover, when the number of twists is greater than 4000 T / m, the single fiber breakage is suppressed, but the strong twisted yarn constituting the woven fabric or knitted fabric becomes too hard, and thus tends to cause hardening of the texture.

  Polyurethane, polyurea, polyurethane / polyurea elastomer, polyacrylic acid, acrylonitrile / butadiene elastomer, styrene / butadiene elastomer, etc. can be used as the polymer elastic body used in the sheet-like material of the present invention. From the viewpoint of properties, polyurethane is preferably used.

  In addition, the polymer elastic body may include polyester-based, polyamide-based, and polyolefin-based elastomer resins, acrylic resins, ethylene-vinyl acetate resins, and the like. The polymer elastic body may be either dissolved in an organic solvent or dispersed in water.

  When using polyurethane as the polymer elastic body, polyurethane having a structure in which polyol, polyisocyanate, and chain extender are appropriately reacted can be used.

  When the polyurethane is an aqueous polyurethane, a hydrophilic group-containing polyurethane can be used. As a component which makes a polyurethane contain hydrophilic group, a hydrophilic group containing active hydrogen component is mentioned, for example. Examples of the hydrophilic group-containing active hydrogen component include compounds containing a nonionic group and / or an anionic group and / or a cationic group and an active hydrogen.

  Examples of the compound having a nonionic group and active hydrogen include triols such as trimethylolpropane and trimethylolbutane.

  In addition, examples of the compound having an anionic group and active hydrogen include carboxyl group-containing compounds such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid and 2,2-dimethylolvaleric acid, and derivatives thereof. , Compounds containing sulfonic acid groups such as 1,3-phenylenediamine-4,6-disulfonic acid, 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid and derivatives thereof, and these compounds Examples include salts neutralized with a neutralizing agent.

  Examples of the compound containing a cationic group and active hydrogen include tertiary amino group-containing compounds such as 3-dimethylaminopropanol, N-methyldiethanolamine, N-propyldiethanolamine, and derivatives thereof.

  The hydrophilic group-containing active hydrogen component can also be used in the form of a salt neutralized with a neutralizing agent.

  By introducing a sulfonic acid group and a carboxyl group, among other hydrophilic group-containing active hydrogen components, into the water-based polyurethane, not only the hydrophilicity of the polyurethane molecule is increased, but also by using a crosslinking agent described later in combination. In addition, a three-dimensional cross-linked structure can be provided in the polyurethane molecule, and the physical properties can be improved more easily.

  Examples of the polyether-based polyol in the above-described polymer polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like, and copolymer polyols obtained by combining them.

  Examples of the polyester-based polyol include polyester polyols obtained by condensing various low molecular weight polyols and polybasic acids, and those obtained by open polymerization of lactones.

  Examples of the low molecular weight polyol include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10- Linear alkylene glycol such as decanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, etc. One or more selected from branched alkylene glycols, alicyclic diols such as 1,4-cyclohexanediol, and aromatic dihydric alcohols such as 1,4-bis (β-hydroxyethoxy) benzene are used. be able to. Further, addition products obtained by adding various alkylene oxides to bisphenol A can also be used.

  Polybasic acids include, for example, succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydro One kind or two or more kinds selected from isophthalic acid can be mentioned.

  Examples of the polylactone polyol include polylactone polyols obtained by ring-opening polymerization of γ-butyrolactone, γ-valerolactone, ε-caprolactone, or the like alone or in a mixture of two or more thereof using a polyhydric alcohol as an initiator.

  Examples of the polycarbonate-based polyol include compounds obtained by a reaction between a polyol and a carbonate compound such as dialkyl carbonate and diaryl carbonate.

  As the polyol as the raw material for producing the polycarbonate-based polyol, the polyols mentioned as the raw material for producing the polyester polyol can be used. As the dialkyl carbonate, dimethyl carbonate, diethyl carbonate and the like can be used, and as the diaryl carbonate, diphenyl carbonate and the like can be mentioned.

  As the chain extender used in the production of polyurethane, compounds used in conventional production of polyurethane can be used, and among them, the molecular weight of 600 or less having two or more active hydrogen atoms capable of reacting with an isocyanate group in the molecule. Low molecular weight compounds are preferably used. Specifically, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanediol, xylylene glycol Diols such as, triols such as trimethylolpropane and trimethylolbutane, hydrazine, ethylenediamine, isophoronediamine, piperazine, 4,4'-methylenedianiline, tolylenediamine, xylylenediamine, hexamethylenediamine, 4, Examples include diamines such as 4′-dicyclohexylmethanediamine, triamines such as diethylenetriamine, and amino alcohols such as aminoethyl alcohol and aminopropyl alcohol.

  Examples of organic polyisocyanates used in the production of polyurethane include aliphatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate (hereinafter sometimes abbreviated as IPDI), water-added xylylene diisocyanate, dicyclohexylmethane diisocyanate ( Hereinafter, alicyclic diisocyanates such as hydrogenated MDI), and aromatics such as xylylene diisocyanate (hereinafter sometimes abbreviated as XDI) and tetramethyl-m-xylylene diisocyanate. / Aliphatic diisocyanate, tolylene diisocyanate (hereinafter sometimes abbreviated as TDI), 4,4′-diphenylmethane diisocyanate (hereinafter sometimes abbreviated as MDI), tolidine diisocyanate, and And aromatic diisocyanates such as naphthalene diisocyanate (hereinafter sometimes abbreviated as NDI).

  The elastic polymer used for the sheet-like material of the present invention has a urethane bond site, sulfonic acid group, carboxyl group, hydroxyl group or primary or secondary amino group, which has high reactivity with a bifunctional or higher compound described later. It is preferable to have.

  The ultraviolet absorber used in the sheet-like material of the present invention may be a known ultraviolet absorber. For example, what can be used in the present invention is a reaction with a crosslinking agent that is a bifunctional or higher compound described later. It contains functional groups that are possible. Examples of such functional groups include those containing active hydrogen such as a hydroxy group, a carboxyl group, and an amino group, and isocyanate groups. An ultraviolet absorber having a maximum absorption wavelength in a wavelength range of 260 nm to 350 nm can be preferably used, and a maximum absorption in a wavelength range of 260 nm to 350 nm such as a so-called hindert type, benzotriazole type, benzotriazine type, or benzophenone type. It has a wavelength. It is particularly preferable to use a benzotriazole type which is relatively low cost, has a wide absorption wavelength range as compared with other ultraviolet absorbers, and can prevent deterioration of polyurethane from visible light.

  As the benzotriazole ultraviolet absorber, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (manufactured by BASF; trade name TINUVIN329), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by BASF; trade name TINUVIN234), 2,2′-methylenebis [6- (2H-benzo Triazol-2-yl) -4-t-octylphenol] (manufactured by ADEKA; LA-31), methyl 3- (3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl ) Propionate / polyethylene glycol 300 reaction product (manufactured by BASF; trade name TINUBIN 1130).

  In the sheet-like material of the present invention, the polymer elastic body is bonded to the ultraviolet absorber by a covalent bond, and the polymer elastic bodies are bonded to each other by a covalent bond. Since the polymer elastic body and the ultraviolet absorber are covalently bonded, the ultraviolet absorber does not volatilize from the sheet-like material even in a high temperature atmosphere, and the fogging resistance can be greatly improved. Further, since the polymer elastic bodies are covalently bonded to each other, excellent wear characteristics can be imparted to the sheet-like material.

  The covalent bond between the polymer elastic body and the ultraviolet absorber, and the covalent bond between the polymer elastic bodies are, for example, a fibrous base material composed of ultrafine fibers, a polymer elastic body and an ultraviolet absorber, and if necessary Each composition can be covalently bonded by heating at 80 ° C. to 200 ° C. after imparting a bifunctional or higher functional compound.

  In the sheet-like material of the present invention, the polymer elastic body is bonded by a covalent bond via a UV absorber and a bifunctional or higher compound, and the macromolecular elastic bodies are bonded via a bifunctional or higher compound. It is preferable that they are bonded by a covalent bond. By being covalently bonded via the bifunctional or higher compound, both compositions can be easily covalently bonded even when the reactivity between the polymer elastic body and the ultraviolet absorber is low, so that the composition is stronger. It is preferable in that a covalent bond is easily obtained. As the bifunctional or higher compound, a known compound widely used as a crosslinking agent is used which forms a crosslinked structure by a covalent bond with a functional group of a polymer elastic body and an ultraviolet absorber. I can do it. Below, the compound more than bifunctional may be described as a crosslinking agent.

  As the crosslinking agent, one having at least one reactive group in the molecule that reacts with a reactive group introduced into the polymer elastic body and one reactive group that reacts with an ultraviolet absorber can be used. Specifically, a polyisocyanate-based crosslinking agent, a melamine-based crosslinking agent, an oxazoline-based crosslinking agent, a carbodiimide-based crosslinking agent, an aziridine-based crosslinking agent, an epoxy crosslinking agent, a hydrazine-based crosslinking agent, and the like can be given. A crosslinking agent may be used individually by 1 type, and can also use 2 or more types together.

  The water-soluble isocyanate compound has two or more isocyanate groups in the molecule, and examples thereof include the organic polyisocyanate-containing compounds. Examples of commercially available products include “Baihijoule” (registered trademark) series, “Death Module” (registered trademark) series, and the like manufactured by Bayer MaterialScience.

  The blocked isocyanate compound has two or more blocked isocyanate groups in the molecule. The blocked isocyanate group means a group obtained by blocking the organic polyisocyanate compound with a blocking agent such as amines, phenols, imines, mercaptans, pyrazoles, oximes and active methylenes. The commercial products include “Elastoron” (registered trademark) series of Daiichi Kogyo Seiyaku Co., Ltd., “Duranate” (registered trademark) series manufactured by Asahi Kasei Chemicals Corporation, and “Takenate” (manufactured by Mitsui Chemicals, Inc.). Registered trademark) series and the like.

  Examples of the melamine-based crosslinking agent include compounds having two or more methylol groups or methoxymethylol groups in the molecule. Commercially available products include “Uban” (registered trademark) series manufactured by Mitsui Chemicals, “Cymel” (registered trademark) series manufactured by Nippon Cytec Co., Ltd., and “Sumimar” (registered trademark) manufactured by Sumitomo Chemical Co., Ltd. ) Series.

  Examples of the oxazoline-based crosslinking agent include compounds having two or more oxazoline groups (oxazoline skeletons) in the molecule. Examples of commercially available products include “Epocross” (registered trademark) series manufactured by Nippon Shokubai Co., Ltd. Examples of the carbodiimide-based crosslinking agent include compounds having two or more carbodiimide groups in the molecule. Examples of the commercial products include “Carbodilite” (registered trademark) series manufactured by Nisshinbo Industries, Ltd.

  Examples of the epoxy-based crosslinking agent include compounds having two or more epoxy groups in the molecule. Examples of commercially available products include “Denacol” (registered trademark) series manufactured by Nagase Chemtech, diepoxy / polyepoxy compounds manufactured by Sakamoto Pharmaceutical Co., Ltd., and “EPICRON” (registered trademark) series manufactured by DIC.

  Examples of the aziridine-based crosslinking agent include compounds having two or more aziridinyl groups in the molecule. Examples of the hydrazine-based crosslinking agent include hydrazine and compounds having two or more hydrazine groups (hydrazine skeleton) in the molecule.

The sheet-like material of the present invention has a fogging characteristic of 85% or more and a wear loss of 20,000 times in the Martindale abrasion test. By setting the fogging characteristics to 85% or more, it is possible to suppress volatilization of the ultraviolet absorber even in applications that are exposed to high temperature conditions for a long period of time. Further, by setting the weight loss to 10 mg or less, it is possible to suppress the fiber from dropping off due to friction, and to maintain a good appearance on the surface of the sheet-like material.
<Method for producing sheet-like material>
Next, the manufacturing method of the sheet-like material of this invention is demonstrated.

  The method for producing a sheet-like material according to the present invention is a method for producing a sheet-like material comprising a fibrous base material composed of ultrafine fibers and a polymer elastic body. It is a manufacturing method of a sheet-like thing including the process of heating at 80 ° C-200 ° C, after giving a ultraviolet absorber and a compound more than bifunctional.

  In the method for producing a sheet-like product of the present invention, the fibrous base material made of ultrafine fibers is a nonwoven fabric formed by entanglement of ultrafine fiber bundles. As means for obtaining the nonwoven fabric composed of the ultrafine fibers, it is preferable to use ultrafine fiber generating fibers such as sea-island type composite fibers. Since it is practically difficult to produce a nonwoven fabric directly from ultrafine fibers, a nonwoven fabric is first produced from ultrafine fiber-generating fibers, and ultrafine fibers are generated from the ultrafine fiber-generating fibers in this nonwoven fabric. A nonwoven fabric in which the bundles are intertwined can be obtained.

  As ultra-fine fiber generation type fiber, two-component thermoplastic resins with different solvent solubility are used for sea component and island component, and the sea component is dissolved and removed using solvent etc., and the island component is made into ultra-fine fiber. It is possible to employ a peelable composite fiber that splits fibers into ultrafine fibers by alternately arranging fibers or two-component thermoplastic resin radially or in a multilayer shape on the fiber cross section, and separating and separating each component. Among these, sea-island type composite fibers are preferable in that ultrafine fibers can be stably obtained.

  For the sea-island type composite fiber, a sea-island type composite fiber that uses a sea-island type composite base to spun the sea component and the island component together, and the sea island that mixes and spins the sea component and the island component There is a type composite fiber, but from the point that ultrafine fibers of uniform fineness can be obtained, and that a sufficiently long ultrafine fiber is obtained and contributes to the strength of the sheet-like material, the sea island using a sea-island type composite base A type composite fiber is particularly preferably used.

  As the sea component of the sea-island composite fiber, polyethylene, polypropylene, polystyrene, copolymerized polyester obtained by copolymerizing sodium sulfoisophthalic acid, polyethylene glycol, or the like, and polylactic acid can be used. The component used as the sea component is preferably a different one from the combined island component in terms of solubility or decomposability with a decomposing agent and having a low compatibility with the island component. Among these, from the viewpoint of stability of the spinning process, polyester and nylon are preferably used as the island component, and polystyrene or copolymer polyester as the sea component is preferably used.

  As island components of sea-island type composite fibers, various synthetic fibers made of polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyamides such as 6-nylon and 66-nylon, acrylic, polyethylene, and polypropylene are used. However, polyester fibers made of polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, etc. are preferably used from the viewpoints of strength, dimensional stability, light resistance and dyeability.

  As described above, as a method for obtaining a nonwoven fabric composed of ultrafine fiber generating fibers used in the method for producing a sheet-like material of the present invention, a method in which a fiber web is entangled with a needle punch or a water jet punch, a spunbond method, a melt blown method A method such as needle punching or water jet punching is preferably used to achieve the above-described ultrafine fiber bundle mode.

  In the present invention, as described above, a short fiber nonwoven fabric obtained by applying these, a long fiber nonwoven fabric obtained from a spunbond method or a melt blow method, a nonwoven fabric obtained by a papermaking method, or the like can be employed. Among them, a short fiber nonwoven fabric is particularly preferably used because it can obtain a good napped fiber length and the like.

  When a nonwoven fabric and a woven fabric made of the ultrafine fiber-generating fiber are laminated and used, a needle punch, a water jet punch or the like is preferably used for lamination and integration from the viewpoint of fiber entanglement. Among these, the needle punch is preferably used because it is not limited to the sheet thickness and the fibers can be oriented in a direction perpendicular to the surface of the nonwoven fabric made of ultrafine fiber-generating fibers.

In the method for producing a sheet-like material according to the present invention, when the ultrafine fiber generating fiber is entangled by needle punching regardless of the combination with the woven fabric, the punch density range is 300 / cm ^{2 to} 6000 / it is preferable to cm ^2, and a more preferred embodiment be a 1000 ^/ cm 2 to 3000 present / cm ^2.

  For the entanglement between the nonwoven fabric and the woven fabric made of ultrafine fiber-generating fibers, the woven fabric is laminated on one or both sides of the nonwoven fabric, or the fabric is sandwiched between a plurality of nonwoven fabrics, and the fibers are entangled with each other by needle punching. It can be set as the non-ultrafine fiber base material. In the present invention, the non-ultrafine fiber base material refers to the entire combination of a non-woven fabric made of ultrafine fiber-generating fibers and a woven fabric when a woven fabric is used. A non-woven fabric composed of generating fibers.

It is preferable that the apparent density of the nonwoven fabric made of the ultrafine fiber generating fiber after the needle punching process or the water jet punching process is 0.15 to 0.30 g / cm ³ . By setting the apparent density to 0.15 g / cm ³ or more, a sheet-like material having sufficient form stability and dimensional stability can be obtained. On the other hand, when the apparent density is 0.30 g / cm ³ or less, a sufficient space for applying the polymer elastic body can be maintained.

  From the viewpoint of densification, it is preferable that the nonwoven fabric made of the ultrafine fiber-generating fibers thus obtained is shrunk by dry heat or wet heat or both, and further densified.

  An ultra-fine fiber is generated from an ultra-fine fiber-generating fiber by dissolving a readily soluble polymer that is a sea component. As the solvent for dissolving the readily soluble polymer which is a sea component, if the sea component is a polyolefin such as polyethylene or polystyrene, an organic solvent such as toluene or trichloroethylene is used, and if the sea component is polylactic acid or a copolyester, An alkaline aqueous solution such as sodium hydroxide can be used. The ultrafine fiber generation processing (sea removal treatment) can be performed by immersing a nonwoven fabric made of ultrafine fiber generation type fibers (fibers that can be made ultrafine) in a solvent and squeezing it.

  In the method for producing a sheet-like material of the present invention, examples of the solvent used when polyurethane is applied as the polymer elastic body include N, N'-dimethylformamide and dimethyl sulfoxide. It can also be used as an aqueous polyurethane solution in which polyurethane is dispersed as an emulsion in water.

  When dipping a fibrous base material in a polymeric elastic body solution in which the polymeric elastic body is dissolved in a solvent, the polymeric elastic body solution is applied to the fibrous base material and then dried to obtain the polymeric elastic body. It is substantially solidified and solidified. In addition, in this invention, when only calling it a fibrous base material, the fibrous base material which consists of a non-ultrafine fiber base material or an ultrafine fiber is represented.

  In the case of a solvent-based polyurethane solution, it can be solidified by dipping in a non-soluble solvent. Further, in the case of an aqueous polyurethane liquid having gelling properties, it can be solidified by gelling and then drying by a dry coagulation method or the like. In drying, the fiber base material and the elastic polymer may be heated at a temperature that does not impair the performance.

  The ultrafine fiber generation processing is performed at any stage after the polymer elastic body is applied to the fiber substrate made of ultrafine fibers, after the polymer elastic body is applied to the non-ultrafine fiber substrate, or after the raising treatment. You may go.

  Regarding the order of the above-mentioned ultrafine fiber generation processing and polymer elastic body application, when performing ultrafine fiber generation processing before polymer elastic body application, polyvinyl alcohol or the like is used so that the ultrafine fiber and the polymer elastic body are not bonded. In order to obtain the flexibility of the sheet-like material, it is preferable to apply a polymer elastic body solution after applying a temporary filler that can be dissolved and removed to the nonwoven fabric, and then removing the temporary filler.

  Further, in the method for producing a sheet-like product of the present invention, in an artificial leather sheet substrate in which a polymer elastic body is applied to a fibrous base material made of ultrafine fibers, the amount of polymer elastic body applied and the ultrafine fiber density are artificial This is important in obtaining a surface in which the ultrafine fiber bundle of the leather sheet substrate is firmly bound by the polymer elastic body.

  As for a suitable use ratio of the polymer elastic body, the mass of the polymer elastic body with respect to the mass of the fibrous base material composed of ultrafine fibers is preferably 10% by mass or more and 120% by mass or less, more preferably 20% by mass or more and 100%. It is below mass%. When the mass of the polymer elastic body is less than 10% by mass, even if the grinding amount is adjusted to a small amount in the raising process of the artificial leather sheet substrate, the fibers are largely dropped, and the surface layer portion has napped portions and surface layer portions. The boundary between exposed polymer elastic body portions may not be clarified. On the other hand, when the mass of the polymer elastic body is more than 120% by mass, the boundary between the napped portion made of ultrafine fibers on the surface layer portion and the polymer elastic body portion exposed on the surface layer portion is clarified by adjusting the grinding amount to a small amount. However, the texture of the sheet-like material may become hard.

  As a method of reacting the polymer elastic body, the ultraviolet absorber, and the crosslinking agent, the polymer elastic dispersion liquid is allowed to contain the ultraviolet absorber and the crosslinking agent, and the solution is impregnated with a fibrous base material composed of ultrafine fibers. Later, a method of heating, or a method of heating by applying an ultraviolet absorber and a crosslinking agent to the artificial leather sheet substrate after solidification of the polymer elastic body can be mentioned. During heating, the polymer elastic body and the ultraviolet absorbent are covalently bonded via a cross-linking agent, so that the volatilization of the ultraviolet absorbent can be significantly suppressed. Furthermore, not only the above reaction, but also the polymer elastic bodies are cross-linked by a cross-linking agent to form a three-dimensional network structure, thereby increasing the molecular weight of the resin and increasing the cross-linking density of the resin. Durability can also be improved.

  As a method for producing the sheet-like product of the present invention, it is important to perform a heat treatment after imparting a polymer elastic body, an ultraviolet absorber, and a bifunctional or higher compound. The polymer elastic body and the ultraviolet absorber are covalently bonded via the bifunctional or higher compound by applying a heat treatment after applying the polymer elastic body, the ultraviolet absorber and the bifunctional or higher compound. I can do it.

  The heat treatment method may be either dry heat conditions or wet heat conditions, but is preferably performed under dry heat conditions because it can be performed simultaneously with the drying step.

  The heating temperature is important to be in the range of 80 ° C to 200 ° C. The heating temperature is more preferably 90 ° C to 180 ° C, and further preferably 100 ° C to 150 ° C. When the heating temperature is below 60 ° C., the crosslinking reaction does not proceed sufficiently. If the heating temperature exceeds 200 ° C., it will be heated to the vicinity of the softening point of the polymer elastic body to be used, the adhesion structure between the polymer elastic body and the fibers will be biased, and the wear characteristics of the sheet will only be reduced. Not. Moreover, the tendency which causes hardening of a texture is shown.

  The addition amount of the crosslinking agent is preferably 0.5% by mass or more and 3.0% by mass or less with respect to the solid content of the polymer elastic body. When the amount is less than 0.5% by mass, the polymer elastic body and a part of the ultraviolet absorber cannot be chemically bonded, and volatilization of the ultraviolet absorber cannot be suppressed. On the other hand, when an amount exceeding 3.0% by mass is added, the texture tends to be hard.

  As content of the ultraviolet absorber in a sheet-like material, it is preferable that it is 0.1 to 5 mass% with respect to a polymer elastic body solid content. If the content of the ultraviolet absorber is less than 0.1% by mass, the ultraviolet absorbing ability is insufficient and the light fastness may be lowered. On the other hand, if it exceeds 5% by mass, the content of the ultraviolet absorber becomes excessive with respect to the crosslinking agent, and there is a possibility that some of the ultraviolet absorber cannot be bonded to the polyurethane.

  Dividing the obtained sheet-like material into half or several pieces in the sheet thickness direction after application of the polymer elastic body is excellent in production efficiency and is a preferred embodiment.

  Before the raising treatment described later, a lubricant such as a silicone emulsion can be applied to the polymer elastic material-imparting sheet. Moreover, applying an antistatic agent before the raising treatment is a preferable aspect in order to make it difficult for the grinding powder generated from the sheet-like material to be deposited on the sandpaper by grinding.

  In order to form napping on the surface of the sheet-like material, napping treatment can be performed. The raising treatment can be performed by a method of grinding using sandpaper, roll sander or the like.

  If the thickness of the sheet-like material is too thin, physical properties such as tensile strength and tearing strength of the sheet-like material will be weak, and if too thick, the texture of the sheet-like material will be hard, so about 0.1 to 5.0 mm Preferably there is.

  The sheet can be dyed. As a dyeing method, it is preferable to use a liquid dyeing machine because the sheet-like material can be softened by dyeing the sheet-like material and at the same time giving a stagnation effect. If the dyeing temperature is too high, the polyurethane may be deteriorated. Conversely, if the dyeing temperature is too low, dyeing of the dye onto the fiber becomes insufficient. Therefore, the dyeing temperature can be set depending on the type of fiber, and generally 80 ° C. or higher and 145 ° C. It is preferable that it is below, More preferably, it is 110 degreeC or more and 130 degrees C or less.

  The dye is selected according to the type of fiber constituting the fibrous base material made of ultrafine fibers. For example, disperse dyes can be used for polyester fibers, acidic dyes or metal-containing dyes can be used for polyamide fibers, and combinations thereof can be used. When dyeing with a disperse dye, reduction washing can be performed after dyeing.

  It is also a preferred embodiment to use a dyeing assistant during dyeing. By using a dyeing assistant, the uniformity and reproducibility of dyeing can be improved. In addition, a finishing treatment using a softening agent such as silicone, an antistatic agent, a water repellent, a flame retardant, a light proofing agent, and an antibacterial agent can be performed in the same bath or after dyeing.

  The sheet-like material of the present invention is mainly used as an artificial leather, and is very useful as a skin material for seats, ceilings, interiors, etc. in automobile interiors such as automobile interior materials, furniture, chairs and wall materials, and trains and airplanes. Interior materials with elegant appearance, shirts, jackets, casual shoes, sports shoes, men's shoes, women's shoes and other shoe uppers, trims, bags, belts, wallets, etc., and clothing materials used for some of them It can be suitably used as industrial materials such as wiping cloth, polishing cloth and CD curtain.

  Next, although an Example is given and the sheet-like material of this invention and its manufacturing method are demonstrated in more detail, this invention is not limited by these Examples.

[Evaluation method]
(1) Light fastness (gray scale value):
Evaluation was made by an accelerated light resistance test method using a xenon lamp.

Equipment name: Atlas 4000, temperature measurement P. T.A. 89 ± 3 ℃, humidity setting 50 ± 5%,
Radiation intensity: 48 to 162 W / m (range of 300 to 400 nm)
Irradiance ratio: 320 nm or less was determined to be less than 1.5% in the range of 300 to 400 nm, and judged with a gray scale for discoloration (JIS L0804).

Judgment is made by changing the color of the sample after light irradiation in 9 steps from 1 to 5 in 0.5 increments. The n number is 3, and the remaining grades except the best and worst grades. The grade was taken as the evaluation result. For example, if the n = 3 grade judgment is grade 3, grade 3 and grade 4, the evaluation result is grade 3, and if grade 3, grade 4 and grade 4, the assessment result is grade 4.
(2) Fogging characteristics:
Three samples with a diameter of 80 cm were collected. A fogging test was performed by heating at 100 ° C. for 20 hours with a glass sag acceleration test apparatus (window screen fogging tester WF-2, manufactured by Suga). Next, the reflectance of the glass plate (110 mm × 110 mm square shape, thickness 3 mm) after the fogging test was measured with a gonioglossometer (manufactured by Suga; UGV-5) using a halogen lamp as a light source. The measurement angle (incident angle and light receiving angle) is 60 degrees, the sample is rotated by 90 degrees, the sample is measured four times (360 degrees in four 90 degrees), and each obtained data R1, As R2, R3, and R4, the reflectance R after the fogging test was calculated by the following equation.

R = (R1 + R2 + R3 + R4) / 4
The fogging characteristic was obtained from the R value and the following R0 value according to the following equation.

Fogging characteristics (%) = R / R0 × 100
That is, here, R1, R2, R3, and R4 are the reflectance (%) of the glass plate after the fogging test, R is the average value of R1, R2, R3, and R4, and R0 is the glass before the fogging test. It is the reflectance (%) of the plate. The average value was calculated by setting the number of n to 3 (3 samples) and rounded off after the decimal point.
(3) Pilling evaluation:
Martindale wear evaluation (durability evaluation) was performed. As a Martindale abrasion tester, James H. Heal & Co. Model 406 made by the company was used. The company's ABRASIVE CLOTH SM25 was used as a standard friction cloth. After applying a load equivalent to 12 kPa to the sheet-like material sample and rubbing it under the condition of 20,000 wear times, the appearance of the sheet-like material was visually observed and evaluated. The evaluation criteria were grade 5 when the appearance of the sheet-like material was not changed from before the friction, grade 1 when a lot of pills were generated, and grade 0.5 between them. Grades 4 through 5 were accepted.
(4) Loss of wear The same operation as the above-described pilling evaluation is performed, and the weight before and after friction is used to calculate the following formula:
Wear loss (mg) = weight before friction (mg)-weight after friction (mg)
From this, the weight loss (mg) was calculated.
(5) Texture 10 healthy adult men and 10 adult women each, with a total of 20 evaluators, the following evaluations were made by tactile sensation. A good level of the present invention was "A" or "B".
A: Very flexible.
○: Flexible.
Δ: Hard x: Very hard
[Notation of chemical substances]
PU: Polyurethane PTMG: Polytetramethylene glycol PCL with number average molecular weight 2000: Polycaprolactone PHMPC with number average molecular weight 2000: Derived from 1,6-hexanediol and 3-methyl-1,5-pentanediol with number average molecular weight 2000 Copolycarbonate diol MDI: 4,4′-diphenylmethane diisocyanate H12 MDI: dicyclohexylmethane diisocyanate DMF: N, N-dimethylformamide PET: polyethylene terephthalate PVA: polyvinyl alcohol <Example 1>
[Types of polyurethane]
Composition of organic solvent polyurethane I (PU-I) Polyisocyanate: MDI
Polyol: PTMG 70%, PCL 30%
Chain extender: EG
[Manufacture of sheets]
After melt spinning at an island / sea mass ratio of 55/45 using PET as the island component and polystyrene as the sea component and a sea-island type composite die having 36 islands, after stretching and crimping, 51 mm To obtain a raw material of sea-island type composite fiber having a single fiber fineness of 3.1 dtex.

Using this raw material of sea-island type composite fiber, a fiber web was formed through a card and cross wrapping process, and needle punched with a punch number of 600 / cm ² to obtain a nonwoven fabric made of ultrafine fiber-generating fibers. Insert a fabric made of polyester fiber above and below a nonwoven fabric made of ultrafine fiber generation type fibers, apply needle punch with a punch number of 2900 / cm ² , and bond the nonwoven fabric made of ultrafine fiber generation type fibers and the fabric to make it non-fine A fibrous base material was obtained.

  This non-fine fiber base material is shrunk with 96 ° C. hot water, impregnated with 5% PVA aqueous solution, and dried with hot air at a drying temperature of 110 ° C. for 10 minutes. PVA was applied so that the PVA mass relative to the mass was 4% by mass. The sea component of the non-ultrafine fiber base material provided with this PVA was dissolved and removed in trichlorethylene to obtain a sea removal sheet formed by entanglement of the ultrafine fiber and the fabric, that is, a fiber base material made of ultrafine fiber. . The average single fiber fineness was 0.05 detex by observation with a scanning electron microscope (SEM) of the cross section of the seawater-removed sheet.

  2- (2H-benzoic acid), which is a benzotriazole-based ultraviolet absorber for polyurethane (PU-I) prepared by adjusting the fibrous base material composed of ultrafine fibers to a solid content concentration of 12% and the solid content of the polyurethane. 2% by mass of triazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by BASF; trade name TINUVIN234) and Mitsui Chemicals, Ltd., which is a blocked isocyanate crosslinking agent “Takenate” manufactured by the method was impregnated in a DMF solution prepared to give 3% by mass relative to the mass of polyurethane, and the polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Thereafter, PVA and DMF were removed with hot water, and hot air drying was performed at 140 ° C. for 10 minutes to give polyurethane so that the mass of polyurethane relative to the mass of the fibrous base material composed of ultrafine fibers of the sheet-like material was 20% by mass. .

  And it cut in half in the thickness direction, and raised surfaces were formed by grinding the half-cut surface using an endless sandpaper whose sandpaper count was 240. Furthermore, after performing shrinkage treatment and dyeing simultaneously at 130 ° C. with a liquid flow dyeing machine, drying was carried out with a dryer to obtain a sheet-like material.

  As shown in Table 1, the fogging characteristics, light fastness, pilling evaluation, wear loss, and texture of the obtained sheet-like material were all good.

<Example 2>
The same treatment as in Example 1 was carried out except that the aziridine-based crosslinking agent “Chemite” manufactured by Nippon Shokubai Co., Ltd. was used as the crosslinking agent, and the heating temperature was 80 ° C. after removing PVA and DMF with hot water. A sheet was obtained.

As shown in Table 1, the obtained sheet-like material had good fogging characteristics, light fastness, pilling evaluation, wear loss, and texture.
<Example 3>
After removing PVA and DMF with hot water, the same treatment as in Example 1 was performed except that the heating temperature was 200 ° C., and a sheet-like material was obtained.

As shown in Table 1, the obtained sheet-like material had good fogging characteristics, light fastness, pilling evaluation, wear loss, and texture.
<Example 4>
A sheet-like material was obtained in the same manner as in Example 1 except that CHIMASSORB 81 (manufactured by BASF), which is a benzophenone-based ultraviolet absorber, was used as the ultraviolet absorber.

As shown in Table 1, fogging characteristics, pilling evaluation, wear loss, and texture of the obtained sheet-like material were good, but the light fastness was slightly worse than that of Example 1.
<Comparative Example 1>
Except that no crosslinking agent was added, the same treatment as in Example 1 was performed to obtain a sheet.

  As shown in Table 2, although the pilling evaluation, texture, and light fastness of the obtained sheet-like material were good, the wear loss and fogging characteristics were poor.

<Comparative example 2>
A sheet-like material was obtained by performing the same treatment as in Example 1 except that no ultraviolet absorber was added.

As shown in Table 2, fogging characteristics, pilling evaluation, wear loss, and texture of the obtained sheet-like material were good, but light fastness was poor.
<Comparative Example 3>
Except that PVA and DMF were removed with hot water and the hot-air drying conditions were 210 ° C. and 10 minutes, the same treatment as in Example 1 was performed to obtain a sheet.

As shown in Table 2, the light fastness of the obtained sheet-like material was good, but the fogging characteristics, pilling characteristics, wear loss, and texture were poor.
<Comparative Example 4>
Except that PVA and DMF were removed with hot water and the hot air drying conditions were 50 ° C. and 10 minutes, the same treatment as in Example 1 was performed to obtain a sheet.

As shown in Table 2, the texture, light fastness, pilling evaluation, and weight loss of the obtained sheet-like material were good, but the fogging characteristics were bad.
<Comparative Example 5>
A sheet-like material was obtained by carrying out the same treatment as in Example 1 except that the ultraviolet absorber was not added at the time of impregnation with polyurethane and an ultraviolet absorber was added after dyeing.

  As shown in Table 2, the light-fastness, pilling evaluation, wear reduction, and texture of the obtained sheet-like material were good, but the fogging characteristics were bad.

Claims (3)

  In a sheet-like material comprising a fibrous base material composed of ultrafine fibers and a polymer elastic body, the polymer elastic body is bonded to the ultraviolet absorber by a covalent bond, and the polymer elastic bodies are bonded to each other by a covalent bond. A sheet-like material that is bonded, has a fogging characteristic of 85% or more, and has a weight loss of 10 mg or less after 20,000 Martindale abrasion tests.   The polymer elastic body is covalently bonded to the ultraviolet absorber through a bifunctional or higher compound, and the polymer elastic bodies are bonded to each other via a bifunctional or higher functional compound. The sheet-like material according to claim 1.   In the manufacturing method of the sheet-like material containing the fibrous base material which consists of an ultrafine fiber, and a polymeric elastic body, the polymeric elastic body, the ultraviolet absorber, and the compound more than bifunctional are added to the fibrous base material which consists of an ultrafine fiber. The manufacturing method of a sheet-like thing including the process heated at 80 to 200 degreeC after providing.